EP3920275A1 - Matériau actif d'électrode positive pour batteries au lithium-ion tout solide, électrode et batterie au lithium-ion tout solide - Google Patents
Matériau actif d'électrode positive pour batteries au lithium-ion tout solide, électrode et batterie au lithium-ion tout solide Download PDFInfo
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- EP3920275A1 EP3920275A1 EP20727134.7A EP20727134A EP3920275A1 EP 3920275 A1 EP3920275 A1 EP 3920275A1 EP 20727134 A EP20727134 A EP 20727134A EP 3920275 A1 EP3920275 A1 EP 3920275A1
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
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- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/74—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by peak-intensities or a ratio thereof only
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- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2006/40—Electric properties
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
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- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
- H01M2300/0071—Oxides
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a positive electrode active material for an all-solid-state lithium-ion battery, an electrode, and an all-solid-state lithium-ion battery.
- All-solid-state lithium-ion secondary batteries have advantages such as a higher energy density, a wider operation temperature range, and less deterioration than conventional lithium-ion secondary batteries using electrolytic solutions. For this reason, all-solid-state lithium-ion secondary batteries are attracting attention as nextgeneration energy storage devices.
- Patent Literature 1 describes an all-solid-state lithium-ion secondary battery using LiNi 1/3 Mn 1/3 Co 1/3 O 2 as a positive electrode active material.
- LiNi 1/3 Mm 1/3 Co 1/3 O 2 is a well-known material as a positive electrode active material for a liquid-based lithium-ion secondary battery.
- lithium ions are exchanged between a positive electrode active material and a solid electrolyte.
- a positive electrode active material capable of smoothly performing the above exchanging of lithium ions and improving battery performance.
- the present invention was made in order to such circumstances, and an object of the present invention is to provide a positive electrode active material for an all-solid-state lithium-ion battery capable of smoothly performing exchanging of lithium ions between a positive electrode and a solid electrolyte and improving battery performance. Furthermore, another object of the present invention is to provide an electrode and an all-solid-state lithium-ion battery having such a positive electrode active material for an all-solid-state lithium-ion battery.
- the present invention includes the following aspects.
- a positive electrode active material for an all-solid-state lithium-ion battery includes particles including crystals of a lithium metal composite oxide.
- the positive electrode active material for an all-solid-state lithium-ion battery may be used for an all-solid-state lithium-ion battery including an oxide solid electrolyte.
- the transition metal may be at least one selected from the group consisting of Ni, Co, Mn, Ti, Fe, V, and W.
- the lithium metal composite oxide may be represented by the following Formula (1): Li[Li x (Ni (1-y-z-w) Co y Mn z M w ) 1-x ]O 2 (1) (where M is at least one element selected from the group consisting of Fe, Cu, Ti, Mg, Al, W, B, Mo, Nb, Zn, Sn, Zr, Ga, and V and ⁇ 0.10 ⁇ x ⁇ 0.30, 0 ⁇ y ⁇ 0.40, 0 ⁇ z ⁇ 0.40, and 0 ⁇ w ⁇ 0.10 are satisfied).
- the particles may be composed of primary particles, secondary particles formed of an agglomeration of the primary particles, and single particles present independently of the primary particles and the secondary particles, and the content of the single particles in the particles may be 20% or more.
- the particles may have a coated layer of a metal composite oxide on a surface of each of the particles.
- An electrode includes: the positive electrode active material for an all-solid-state lithium-ion battery according to any one of [1] to [7].
- the electrode may further include a solid electrolyte.
- An all-solid-state lithium-ion battery includes: a positive electrode; a negative electrode; and a solid electrolyte layer disposed between the positive electrode and the negative electrode, wherein the solid electrolyte layer includes a first solid electrolyte, the positive electrode includes a positive electrode active material layer in contact with the solid electrolyte layer and a current collector on which the positive electrode active material layer is laminated, and the positive electrode active material layer includes the positive electrode active material for an all-solid-state lithium-ion battery according to any one of [1] to [7] or the electrode according to [8] or [9].
- the positive electrode active material layer may include the positive electrode active material for an all-solid-state lithium-ion battery and a second solid electrolyte.
- the first solid electrolyte and the second solid electrolyte may be formed of the same substance.
- the first solid electrolyte may have a non-crystalline structure.
- the first solid electrolyte may be an oxide solid electrolyte.
- a positive electrode active material for an all-solid-state lithium-ion battery capable of smoothly performing exchanging of lithium ions between a positive electrode and a solid electrolyte and improving battery performance. Furthermore, it is possible to provide an electrode and an all-solid-state lithium-ion battery having such a positive electrode active material for an all-solid-state lithium-ion battery.
- the positive electrode active material for an all-solid-state lithium-ion battery in this embodiment includes particles containing crystals of a lithium metal composite oxide.
- the particles of the lithium metal composite oxide having the coated layer correspond to "particles containing crystals of a lithium metal composite oxide" related to an aspect of the present invention.
- the particles of the lithium metal composite oxide correspond to "particles containing crystals of a lithium metal composite oxide" related to an aspect of the present invention.
- the positive electrode active material for an all-solid-state lithium-ion battery in this embodiment is a positive electrode active material used for an all-solid-state lithium-ion battery including an oxide solid electrolyte.
- the positive electrode active material for an all-solid-state lithium-ion battery in this embodiment may be simply referred to as a "positive electrode active material" in some cases.
- the positive electrode active material in this embodiment satisfies the following requirements.
- the lithium metal composite oxide included in the positive electrode active material includes a layered structure and includes at least Li and a transition metal.
- the lithium metal composite oxide included in the positive electrode active material in this embodiment contains at least one selected from the group consisting of Ni, Co, Mn, Ti, Fe, V, and W as a transition metal.
- the lithium metal composite oxide included in the positive electrode active material in this embodiment includes at least one selected from the group consisting of Ni, Co, and Mn as a transition metal, the obtained lithium metal composite oxide forms a stable crystal structure from/to which Li ions are able to be removed or inserted. For this reason, in a case in which the positive electrode active material in this embodiment is used for a positive electrode of a secondary battery, a high initial charge and discharge efficiency is obtained. A method for measuring initial charge and discharge efficiency will be described later.
- the lithium metal composite oxide included in the positive electrode active material in this embodiment includes at least one selected from the group consisting of Ti, Fe, V, and W, a crystal structure of the obtained lithium metal composite oxide is strong.
- the positive electrode active material in this embodiment is a positive electrode active material having a high thermal stability. Furthermore, the positive electrode active material in this embodiment has improved cycle characteristics.
- the lithium metal composite oxide is represented by the following Composition Formula (1): Li[Li x (Ni (1-y-z-w) Co y Mn z M w ) 1-x ]O 2 (1) (here, M is one or more elements selected from the group consisting of Fe, Cu, Ti, Mg, Al, W, B, Mo, Nb, Zn, Sn, Zr, Ga, La, and V and ⁇ 0.1 ⁇ x ⁇ 0.30, 0 ⁇ y ⁇ 0.40, 0 ⁇ z ⁇ 0.40, and 0 ⁇ w ⁇ 0.10 are satisfied).
- x in Composition Formula (1) is preferably more than 0, more preferably 0.01 or more, and still more preferably 0.02 or more. Furthermore, in order to obtain an all-solid-state lithium-ion battery having a higher initial coulomb efficiency, x in Composition Formula (1) is preferably 0.25 or less, and more preferably 0.10 or less.
- excellent cycle characteristics means characteristics in which an amount of decrease in battery capacity when charging and discharging are repeatedly performed is small and means that a ratio of a discharge capacity at the time of re-measurement to an initial discharge capacity does not easily decrease.
- the all-solid-state lithium-ion battery is charged by applying a negative potential to a positive electrode and a positive potential to a negative electrode through an external power supply.
- the all-solid-state lithium-ion battery can also be discharged by connecting a discharge circuit to the positive electrode and the negative electrode of the charged all-solid-state lithium-ion battery and supplying electricity to the discharge circuit.
- the discharge circuit includes an electronic device, an electric device, and an electric vehicle driven through electric power of the all-solid-state lithium-ion battery.
- initial coulomb efficiency is a value obtained by (initial discharge capacity)/(initial charge capacity) ⁇ 100 (%).
- a secondary battery having a high initial coulomb efficiency has a small irreversible capacity at the time of initial charging and discharging and a capacity per volume and mass relatively easily increases.
- x may be -0.10 or more and 0.25 or less or -0.10 or more and 0.10 or less.
- x may be more than 0 and 0.30 or less, more than 0 and 0.25 or less, or more than 0 and 0.10 or less.
- x may be 0.01 or more and 0.30 or less, 0.01 or more and 0.25 or less, or 0.01 or more and 0.10 or less.
- x may be 0.02 or more and 0.3 or less, 0.02 or more and 0.25 or less, or 0.02 or more and 0.10 or less.
- x is preferably 0 ⁇ x ⁇ 0.30.
- y in the foregoing Composition Formula (1) is preferably more than 0, more preferably 0.005 or more, still more preferably 0.01 or more, and particularly preferably 0.05 or more. Furthermore, in order to obtain a lithium secondary battery having a high thermal stability, y in the foregoing Composition Formula (1) is more preferably 0.35 or less, still more preferably 0.33 or less, and yet more preferably 0.30 or less.
- y may be 0 or more and 0.35 or less, 0 or more and 0.33 or less, or 0 or more and 0.30 or less.
- y may be more than 0 and 0.40 or less, more than 0 and 0.35 or less, more than 0 and 0.33 or less, or more than 0 and 0.30 or less.
- y may be 0.005 or more and 0.40 or less, 0.005 or more and 0.35 or less, 0.005 or more and 0.33 or less, or 0.005 or more and 0.30 or less.
- y may be 0.01 or more and 0.40 or less, 0.01 or more and 0.35 or less, 0.01 or more and 0.33 or less, or 0.01 or more and 0.30 or less.
- y may be 0.05 or more and 0.40 or less, 0.05 or more and 0.35 or less, 0.05 or more and 0.33 or less, or 0.05 or more and 0.30 or less.
- y is preferably 0 ⁇ y ⁇ 0.40.
- x is more preferably 0 ⁇ x ⁇ 0.10 and y is more preferably 0 ⁇ y ⁇ 0.40.
- z in the foregoing Composition Formula (1) is preferably 0.01 or more, more preferably 0.02 or more, and still more preferably 0.1 or more. Furthermore, in order to obtain a lithium secondary battery having a high storage stability at a high temperature (for example, in an environment of 60°C), z in the foregoing Composition Formula (1) is preferably 0.39 or less, more preferably 0.38 or less, and still more preferably 0.35 or less.
- z may be 0 or more and 0.39 or less, 0 or more and 0.38 or less, or 0 or more and 0.35 or less.
- z may be 0.01 or more and 0.40 or less, 0.01 or more and 0.39 or less, 0.01 or more and 0.38 or less, or 0.01 or more and 0.35 or less.
- z may be 0.02 or more and 0.40 or less, 0.02 or more and 0.39 or less, 0.02 or more and 0.38 or less, or 0.02 or more and 0.35 or less.
- z may be 0.10 or more and 0.40 or less, 0.10 or more and 0.39 or less, 0.10 or more and 0.38 or less, or 0.10 or more and 0.35 or less.
- z is preferably 0.02 ⁇ z ⁇ 0.35.
- w in the foregoing Composition Formula (1) is preferably more than 0, more preferably 0.0005 or more, and still more preferably 0.001 or more. Furthermore, in order to obtain a lithium secondary battery having a large discharge capacity at a high current rate, w in the foregoing Composition Formula (1) is preferably 0.09 or less, more preferably 0.08 or less, and still more preferably 0.07 or less.
- w may be 0 or more and 0.09 or less, 0 or more and 0.08 or less, or 0 or more and 0.07 or less.
- w may be more than 0 and 0.10 or less, more than 0 and 0.09 or less, more than 0 and 0.08 or less, or more than 0 and 0.07 or less.
- w may be 0.0005 or more and 0.10 or less, 0.0005 or more and 0.09 or less, 0.0005 or more and 0.08 or less, or 0.0005 or more and 0.07 or less.
- w may be 0.001 or more and 0.10 or less, 0.001 or more and 0.09 or less, 0.001 or more and 0.08 or less, or 0.001 or more and 0.07 or less.
- w is preferably 0 ⁇ w ⁇ 0.07.
- y+z+w in the foregoing Composition Formula (1) is preferably 0.50 or less, more preferably 0.48 or less, and still more preferably 0.46 or less. Furthermore, y+z+w is preferably 0.07 or more.
- 1-y-z-w is preferably 0.50 ⁇ 1-y-z-w ⁇ 0.97, more preferably 0.52 ⁇ 1-y-z-w ⁇ 0.97, and still more preferably 0.54 ⁇ 1-y-z-w ⁇ 0.97.
- the lithium metal composite oxide included in the positive electrode active material in this embodiment satisfy 0.50 ⁇ 1-y-z-w ⁇ 0.97 and 0 ⁇ y ⁇ 0.30 in Composition Formula (1). That is to say, it is desirable that the lithium metal composite oxide included in the positive electrode active material in this embodiment include Ni having a content molar ratio of 0.50 or more and Co having a content molar ratio of 0.30 or less in Composition Formula (1).
- M in the foregoing Composition Formula (1) represents one or more elements selected from the group consisting of Fe, Cu, Ti, Mg, Al, W, B, Mo, Nb, Zn, Sn, Zr, Ga, La, and V.
- M in Composition Formula (1) is preferably one or more elements selected from the group consisting of Ti, Mg, Al, W, B, and Zr, and more preferably one or more elements selected from the group consisting of Al and Zr. Furthermore, in order to obtain a lithium secondary battery having a high thermal stability, M is preferably one or more elements selected from the group consisting of Ti, Al, W, B, and Zr.
- x is 0.02 or more and 0.30 or less
- y is 0.05 or more and 0.30 or less
- z is 0.02 or more and 0.35 or less
- w is 0 or more and 0.07 or less.
- a crystal structure of a lithium metal composite oxide is a layered structure.
- the crystal structure of the lithium metal composite oxide is more preferably a hexagonal crystal structure or a monoclinic crystal structure.
- the hexagonal crystal structure belongs to any one space group selected from the group consisting of P3, P3 1 , P3 2 , R3, P-3, R-3, P312, P321, P3 1 12, P3 1 21, P3 2 12, P3 2 21, R32, P3m1, P31m, P3c1, P31c, R3m, R3c, P-31m, P-31c, P-3m1, P-3c1, R-3m, R-3c, P6, P6 1 , P6 5 , P6 2 , P6 4 , P6 3 , P-6, P6/m, P6 3 /m, P622, P6i22, P6 5 22, P6 2 22, P6 4 22, P6 3 22, P6mm, P6cc, P6 3 cm, P6 3 mc, P-6m2, P-6c2, P-62m, P-62c, P6/mmm, P6/mcc, P6 3 /mcm, and P6 3 /mmc.
- the monoclinic crystal structure belongs to any one space group selected from the group consisting of P2, P2i, C2, Pm, Pc, Cm, Cc, P2/m, P2i/m, C2/m, P2/c, P2i/c, and C2/c.
- a crystal structure is particularly preferably a hexagonal crystal structure belonging to a space group R-3m or a monoclinic crystal structure belonging to C2/m.
- a "cumulative particle size distribution base on a volume” can be measured through a measuring method using a laser diffraction scattering method as a measurement principle.
- a particle size distribution measurement using the laser diffraction scattering method as a measurement principle is referred to as a "laser diffraction type particle size distribution measurement.”
- the cumulative particle size distribution of the positive electrode active material was measured through the following measuring method.
- a dispersion liquid is obtained by adding 0.1 g of a positive electrode active material to 50 ml of a 0.2 mass% aqueous sodium hexametaphosphate solution and dispersing the positive electrode active material.
- a cumulative particle size distribution curve base on a volume is obtained by measuring a particle size distribution of the obtained dispersion solution using a laser diffraction scattering particle size distribution measurement device (for example, Micro Truck MT3300EXII manufactured by MicrotracBEL Corp.).
- a measurement range of the particle size distribution is 0.02 ⁇ m or more and 2000 ⁇ m or less.
- a value of a particle diameter at a point at which a cumulative volume from a fine particle side is 10% is assumed to be a 10% cumulative volume particle size Dio (unit: ⁇ m)
- a value of a particle diameter at a point at which the cumulative volume from the fine particle side is 50% is assumed to be a 50% cumulative volume particle size Dso (unit: ⁇ m)
- a value of a particle diameter at a point at which the cumulative volume from the fine particle side is 90% is assumed to be a 90% cumulative volume particle size D 90 (unit: ⁇ m).
- (D 90 -D 10 )/D 50 is preferably 0.91 or more, more preferably 1.0 or more, still more preferably 1.2 or more, and further still more preferably 1.5 or more.
- (D 90 -D 10 )/D 50 is preferably 11.0 or less, more preferably 10.0 or less, and still more preferably 6.5 or less.
- (D 90 -D 10 )/D 50 may be 0.9 or more and 11.0 or less, 0.9 or more and 10.0 or less, or 0.9 or more and 6.5 or less.
- (D 90 -D 10 )/D 50 may be 0.91 or more and 11.0 or less, 0.91 or more and 10.0 or less, or 0.91 or more and 6.5 or less.
- (D 90 -D 10 )/D 50 may be 1.0 or more and 11.0 or less, 1.0 or more and 10.0 or less, or 1.0 or more and 6.5 or less.
- (D 90 -D 10 )/D 50 may be 1.2 or more and 11.0 or less, 1.2 or more and 10.0 or less, or 1.2 or more and 6.5 or less.
- (D 90 -D 10 )/D 50 may be 1.5 or more and 11.0 or less, 1.5 or more and 10.0 or less, or 1.5 or more and 6.5 or less.
- a particle size distribution may be prepared by mixing positive electrode active materials of two or more types having different particle diameters.
- a "crystallite size ⁇ " and a “crystallite size ⁇ " can be measured using a powder X-ray diffraction measurement using a CuKa radiation.
- the crystallite size of the lithium metal composite oxide included in the positive electrode active material was measured through the following measuring method.
- the positive electrode active material in this embodiment is subjected to powder X-ray diffraction measurement using CuKa as a radiation source having a diffraction angle 2 ⁇ in a measurement range of 10° or more and 90° or less.
- a diffraction angle 2 ⁇ in a measurement range of 10° or more and 90° or less.
- the specific powder X-ray diffraction measurement of the positive electrode active material is performed using an X-ray diffraction measurement device (for example, X'Pert PRO manufactured by PANalytical).
- an X-ray diffraction measurement device for example, X'Pert PRO manufactured by PANalytical.
- a crystallite size ⁇ and a crystallite size ⁇ are calculated through the Scherrer equation using the obtained half-widths.
- a crystallite size ratio ⁇ / ⁇ is obtained from the obtained crystallite size ⁇ and crystallite size ⁇ .
- lithium metal composite oxide included in the positive electrode active material in this embodiment is a hexagonal crystal structure belonging to a space group R-3m will be described in more detail below with reference to the drawings as an example.
- Fig. 1 is a schematic diagram of a crystallite having a crystal structure belonging to a space group R-3m.
- a crystallite size in a direction perpendicular to that of a 003 plane corresponds to the crystallite size ⁇ described above.
- a crystallite size in a direction perpendicular to that of a 104 plane corresponds to the crystallite size ⁇ .
- the 003 plane is indicated as (003) and the 104 plane is indicated as (104).
- the positive electrode active material in this embodiment has a crystallite size ratio ⁇ / ⁇ of 1.0 or more. That is to say, in the positive electrode active material in this embodiment, the crystallite of the lithium metal composite oxide included in the positive electrode active material has grown anisotropically in a z-axis direction with respect to x axis or y axis in Fig. 1 .
- the lithium metal composite oxide has the anisotropically grown crystallite, battery performance such as a discharge capacity can be improved.
- the crystallite of the lithium metal composite oxide in which the crystallite size ratio ⁇ / ⁇ is 1.0 or more is assumed to be Case 1 and a flat crystallite in which the crystallite has grown anisotropically in a direction parallel to that of an xy plane in Fig. 1 is assumed to be Case 2, the crystallite of Case 1 and the crystallite of Case 2 which have the same volume are compared.
- the crystallite of Case 1 has a distance to a center of the crystallite shorter than that of the crystallite of Case 2. For this reason, in the crystallite of Case 1, the movement of Li accompanied by charging and discharging occurs easily.
- ⁇ / ⁇ is preferably 1.2 or more, and more preferably 1.5 or more. Furthermore, ⁇ / ⁇ is preferably 3.0 or less, and more preferably 2.5 or less.
- ⁇ / ⁇ may be 1.0 or more and 3.0 or less, 1.2 or more and 3.0 or less, or 1.5 or more and 3.0 or less.
- ⁇ / ⁇ may be 1.0 or more and 2.5 or less, 1.2 or more and 2.5 or less, or 1.5 or more and 2.5 or less.
- a crystallite size ⁇ is preferably 400 ⁇ or more and 1200 ⁇ or less, more preferably 1100 ⁇ or less, still more preferably 1000 ⁇ or less, further more preferably 900 ⁇ or less, and particularly preferably 840 ⁇ or less. Furthermore, in order to obtain a lithium secondary battery having a high charge capacity, a crystallite size ⁇ is preferably 450 ⁇ or more, and more preferably 500 ⁇ or more.
- ⁇ may be 400 ⁇ or more and 1100 ⁇ or less, 400 ⁇ or more and 1000 or less, or 400 ⁇ or more and 900 ⁇ or less.
- ⁇ may be 450 ⁇ or more and 1200 ⁇ or less, 450 ⁇ or more and 1100 ⁇ or less, 450 ⁇ or more and 1000 or less, or 450 ⁇ or more and 900 ⁇ or less.
- ⁇ may be 500 ⁇ or more and 1200 ⁇ or less, 500 ⁇ or more and 1100 ⁇ or less, 500 ⁇ or more and 1000 or less, or 500 ⁇ or more and 900 ⁇ or less.
- a crystallite size ⁇ is preferably 600 ⁇ or less, more preferably 550 ⁇ or less, still more preferably 500 ⁇ or less, and particularly preferably 450 ⁇ or less. Furthermore, in order to obtain a lithium secondary battery having a high charge capacity, the crystallite size ⁇ is preferably 200 ⁇ or more, more preferably 250 ⁇ or more, and still more preferably 300 ⁇ or more.
- ⁇ may be 200 ⁇ or more and 600 ⁇ or less, 200 ⁇ or more and 550 or less, 200 ⁇ or more and 500 ⁇ or less, or 200 ⁇ or more and 450 ⁇ or less.
- ⁇ may be 250 ⁇ or more and 600 ⁇ or less, 250 ⁇ or more and 550 or less, 250 ⁇ or more and 500 ⁇ or less, or 250 ⁇ or more and 450 ⁇ or less.
- ⁇ may be 300 ⁇ or more and 600 ⁇ or less, 300 ⁇ or more and 550 or less, 300 ⁇ or more and 500 ⁇ or less, or 300 ⁇ or more and 450 ⁇ or less.
- the inventors conducted studies on the basis of such knowledge specific to an all-solid-state lithium-ion battery it was found that, when the positive electrode active material in this embodiment satisfying the above Requirements 1 to 3 is used for the positive electrode of the all-solid-state lithium-ion battery, a high initial charge capacity is measured.
- the positive electrode active material in this embodiment also satisfies Requirement 2.
- the positive electrode active material exchanges lithium ions between the positive electrode active material and a solid electrolyte.
- the positive electrode active material since the positive electrode active material has a wide particle size distribution satisfying Requirement 2, a contact area between the positive electrode active material or the positive electrode active material and the solid electrolyte easily increases.
- the positive electrode active material in this embodiment easily exchanges lithium ions between the positive electrode active material and a solid electrolyte when used for the positive electrode of the all-solid-state lithium-ion battery.
- Requirement 3 means that crystals of the lithium metal composite oxide included in the positive electrode active material grow anisotropically in a lamination direction of a layered structure.
- lithium metal composite oxide satisfying Requirement 3 lithium ions are easily attached and detached between layers from a direction intersecting the lamination direction of the layered structure. For this reason, in the positive electrode active material in this embodiment battery performance is easily improved when satisfying Requirement 3.
- the positive electrode active material in this embodiment satisfying Requirements 1 to 3 can smoothly exchange lithium ions between the positive electrode active material and the solid electrolyte when used for the positive electrode of the all-solid-state lithium-ion battery and improve battery performance.
- a resin binder ethyl cellulose
- a plasticizer dioctyl phthalate
- a solvent acetone
- a positive electrode mixture slurry is obtained by defoaming the obtained slurry using the planetary stirring and air bubble removal device.
- a positive electrode film with a thickness of 50 ⁇ m is formed by applying the obtained positive electrode mixture slurry onto a PET film using a doctor blade and drying the coated film.
- a positive electrode active material sheet with a thickness of 40 ⁇ m is obtained by detaching the positive electrode film from the PET film, subjecting the positive electrode film to punching into a circle with a diameter of 14.5 mm, and uniaxially pressing the positive electrode film at 20 MPa for one minute in a thickness direction thereof.
- a laminate is obtained by laminating a positive electrode active material sheet and a solid electrolyte pellet (for example, manufactured by Toshima Seisakusho Co., Ltd.) made of Li 6.75 La 3 Zr 1.75 Nb 0.25 O 12 and uniaxially pressing them parallel to the lamination direction.
- a solid electrolyte pellet for example, manufactured by Toshima Seisakusho Co., Ltd.
- Organic components are eliminated by heating the positive electrode active material sheet of the obtained laminate and a positive electrode collector (a gold foil; a thickness of 500 ⁇ m) at 300 °C for one hour in a state in which they overlap and are subjected to a pressure of 100 gf. Furthermore, a laminate formed of the solid electrolyte layer and the positive electrode is obtained by increasing a temperature of the positive electrode active material sheet of the obtained laminate and a positive electrode collector to 800 °C at 5 °C/min and then sintering the positive electrode active material sheet of the obtained laminate and a positive electrode collector at 800 °C for one hour.
- a positive electrode collector a gold foil; a thickness of 500 ⁇ m
- the solid electrolyte layer of the laminate of the solid electrolyte layer and the positive electrode, a negative electrode (a Li foil; a thickness of 300 ⁇ m), a negative electrode collector (a stainless steel plate; a thickness of 50 ⁇ m), and a wave washer (made of stainless steel) are also superimposed on each other.
- an all-solid-state lithium-ion battery is prepared by placing the positive electrode on a lower lid of parts for a coin-type battery R2032 (manufactured by Hosen Co., Ltd.), causing the positive electrode, the lower lid, and the wave washer to overlap, using the positive electrode, the lower lid, and the wave washer as an upper lid, and caulking the positive electrode, the lower lid, and the wave washer using a caulking machine.
- a charge and discharge test is performed and initial charge and discharge efficiency is calculated under the following conditions using a half cell prepared through the above-described method.
- Initial charge and discharge efficiency is obtained on the basis of the following calculation formula from the charge capacity and the discharge capacity when charging and discharging are performed under the above conditions.
- Initial charge and discharge efficiency % initial discharge capacity mAh/g initial charge capacity mAh/g ⁇ 100
- particles constituting the positive electrode active material include primary particles, secondary particles formed through agglomeration of the primary particles, and single particles presenting independently of the primary particles and the secondary particles.
- the "primary particles” correspond to particles which do not have grain boundaries in an appearance when observed in a 20,000-fold visual field using a scanning electron microscope and whose particle diameters are less than 0.5 ⁇ m.
- the "secondary particles” correspond to particles which are formed through agglomeration of the primary particles.
- the secondary particles have grain boundaries in an appearance when observed in a 20,000-fold visual field using a scanning electron microscope.
- the "single particles” correspond to particles which are present independently of the secondary particles and do not have grain boundaries on the appearance when observed in a 20000-fold visual field using a scanning electron microscope and whose particle diameters are 0.5 ⁇ m or more.
- the positive electrode active material in this embodiment includes particles which do not have grain boundaries on the appearance and particles which have grain boundaries on the appearance when observed in a 20000-fold visual field using a scanning electron microscope.
- the particles which do not have grain boundaries on the appearance include "primary particles” having particle diameters smaller than a particle diameter of 0.5 ⁇ m and “single particles” having particle diameters larger than the particle diameter of 0.5 ⁇ m.
- the particles which have grain boundaries on the appearance correspond to "secondary particles" which are agglomerates of the "primary particles.”
- the content of the single particles in all of the particles is preferably 20% or more.
- a contact interface between the positive electrode active material and a solid electrolyte is easily secured in a positive electrode layer and lithium ions are smoothly transmitted through an interface.
- the positive electrode active material in which the content of the single particles of all of the particles is 20% or more, grain boundaries are not present in the particles of the single particles of all of the particles. Thus, even when the positive electrode active material is used for the positive electrode of the all-solid-state battery and charging and discharging are repeatedly performed, the particles do not easily break and transmission paths are easily maintained.
- An average particle diameter of the single particles is preferably 0.5 ⁇ m or more, and more preferably 1.0 ⁇ m or more. Furthermore, an average particle diameter of the single particles is preferably 10 ⁇ m or less, and more preferably 5 ⁇ m or less.
- An average particle diameter of the secondary particles is preferably 3.0 ⁇ m or more, and more preferably 5.0 ⁇ m or more. Furthermore, the average particle diameter of the secondary particles is preferably 15 ⁇ m or less, and more preferably 10 ⁇ m or less.
- the average particle diameters of the single particles and the secondary particles can be measured using the following method.
- the positive electrode active material in this embodiment is placed above a conductive sheet stuck above a sample stage. Subsequently, observation is performed in a 20000-fold visual field by irradiating the positive electrode active material with an electron beam with an acceleration voltage of 20 kV using a scanning electron microscope (for example, JSM-5510 manufactured by JEOL Ltd.).
- a scanning electron microscope for example, JSM-5510 manufactured by JEOL Ltd.
- an image of 50 or more and 98 or less single particles or secondary particles is obtained from the obtained electron microscope image (a SEM photograph) using the following method.
- the average particle diameter of the single particles when viewed in a 20000-fold wide visual field, all of the single particles included in one visual field are measurement targets. When the number of single particles included in one visual field is less than 50, the single particles in a plurality of visual fields are measurement targets until the number of measurements is 50 or more.
- the average particle diameter of the secondary particles when viewed in a 20000-fold wide visual field, all of the secondary particles included in one visual field are measurement targets. When the number of secondary particles included in one visual field is less than 50, the secondary particles in a plurality of visual fields are measurement targets until the number of measurements is 50 or more.
- measurement is performed using a distance (a diameter in a fixed direction) between parallel lines drawn from a certain direction when the parallel lines are provided as a particle diameter of the single particles or the secondary particles.
- An arithmetic average value of the obtained particle diameter of the single particles or the secondary particles is an average particle diameter of the single particles included in the positive electrode active material or an average particle diameter of the secondary particles included in the positive electrode active material.
- a coated layer made of a metal composite oxide be provided on surfaces of particles of a lithium metal composite oxide constituting the positive electrode active material.
- an oxide having lithium ion conductivity is used as the metal composite oxide constituting the coated layer.
- the metal composite oxide constituting the coated layer does not have lithium ion conductivity
- the coated layer is very thin (for example, 0.1 nm or more and 1.0 nm or less)
- battery performance is improved as compared with a positive electrode active material which does not have a coated layer.
- lithium ion conductivity is expressed in the coated layer.
- a method for manufacturing a positive electrode active material by attaching a uniform coated layer on the surfaces of the particles of the lithium metal composite oxide by performing control so that the coated layer has a thickness of 0.1 nm or more and 1.0 nm or less is limited to manufacturing methods having poor mass productivity. Examples of such manufacturing methods having poor mass productivity include atomic laser deposition (ALD) methods.
- ALD atomic laser deposition
- the metal composite oxide constituting the coated layer has lithium ion conductivity, even when a thickness of the coated layer is about 5 nm to 20 nm, the coated layer is preferable because it can suitably transmit lithium ions and improve battery performance.
- the thickness of the coated layer can be measured using a positive electrode active material having a maximum diameter of a 50% cumulative volume particle size D50 ( ⁇ m) ⁇ 5% obtained through a laser diffraction type particle size distribution measurement as a target. An arithmetic average value of measured values of 10 particles is defined as a thickness of the coated layer.
- An average thickness of the coated layer of the particles of the positive electrode active material which is a measurement target is obtained based on an analysis result using a scanning transmission electron microscope (STEM)-energy dispersive X-ray spectroscopy (EDX). It is possible to obtain the thickness of the coated layer by creating a line profile of an element specific to the coated layer and setting a range in which the specific element is detected to a range in which the coated layer is present on the basis of the obtained line profile.
- STEM scanning transmission electron microscope
- EDX energy dispersive X-ray spectroscopy
- a metal composite oxide for example, a metal composite oxide with Li and at least one element selected from the group consisting of Nb, Ge, Si, P, Al, W, Ta, Ti, S, Zr, Zn, V, and B can be exemplified.
- the positive electrode active material in this embodiment has the coated layer, it is possible to prevent the formation of a high-resistance layer at the interface between the positive electrode active material and the solid electrolyte and it is possible to realize a high output of the all-solid-state battery. Such an effect is easily obtained in a sulfide-based all-solid-state battery using a sulfide-based solid electrolyte as a solid electrolyte.
- the lithium metal composite oxide contained in the positive electrode active material in this embodiment is manufactured, first, it is desirable that a metal composite compound containing a metal other than lithium among metals constituting the lithium metal composite oxide which is an object be prepared and the prepared metal composite compound be calcined together with an appropriate lithium salt and an inert fusing agent.
- the "metal composite compound” is a compound containing Ni which is an essential metal and any one or more of any metals of Co, Mn, Fe, Cu, Ti, Mg, Al, W, B, Mo, Nb, Zn, Sn, Zr, Ga, La, and V.
- metal composite compound a metal composite hydroxide or a metal composite oxide is preferable.
- a metal composite compound can be manufactured using a commonly known co-precipitation method.
- a commonly known batch type co-precipitation method or a continuous type co-precipitation method can be used.
- the manufacturing method for a metal composite compound will be described in detail below using a metal composite hydroxide including nickel, cobalt, and manganese as an example.
- a metal composite hydroxide represented by Ni a Co b Mn c (OH) 2 is manufactured by causing a nickel salt solution, a cobalt salt solution, a manganese salt solution, and a complexing agent to react together using a co-precipitation method, particularly, the continuous type co-precipitation method described in Japanese Unexamined Patent Application, First Publication No. 2002-201028 .
- a nickel salt which is a solute of the nickel salt solution is not particularly limited, and for example, any one or more of nickel sulfate, nickel nitrate, nickel chloride, and nickel acetate can be used as the nickel salt.
- cobalt salt which is a solute of the cobalt salt solution
- any one or more of cobalt sulfate, cobalt nitrate, cobalt chloride, and cobalt acetate can be used.
- manganese salt which is a solute of the manganese salt solution
- any one or more of manganese sulfate, manganese nitrate, manganese chloride, and manganese acetate can be used.
- the above metal salts are used at a ratio corresponding to a composition ratio of Ni a Co b Mn c (OH) 2 described above. That is to say, the metal salts are used in such a ratio that a molar ratio between nickel in the solute of the nickel salt solution, cobalt in the solute of the cobalt salt solution, and manganese in the solute of the manganese salt solution is a:b:c.
- a solvent for the nickel salt solution, the cobalt salt solution, and the manganese salt solution is water. That is to say, the nickel salt solution, the cobalt salt solution, and the manganese salt solution are aqueous solutions.
- the complexing agent is a compound capable of forming a complex with nickel ions, cobalt ions, and manganese ions in an aqueous solution.
- the complexing agent include ammonium ion donors, hydrazine, ethylenediaminetetraacetic acid, nitrilotriacetic acid, uracil diacetate, and glycine.
- the ammonium ion donors include ammonium salts such as ammonium hydroxide, ammonium sulfate, ammonium chloride, ammonium carbonate, and ammonium fluoride.
- the complexing agent may or may not be used.
- an amount of complexing agents included in a mixed solution including a nickel salt solution, any metal salt solution, and a complexing agent is, for example, a molar ratio of more than 0 and 2.0 or less with respect to the total number of moles of the metal salts.
- an amount of complexing agents included in a mixed solution including a nickel salt solution, a cobalt salt solution, a manganese salt solution, and a complexing agent is, for example, a molar ratio of more than 0 and 2.0 or less with respect to the total number of moles of the metal salts.
- an alkali metal hydroxide is added to the mixed solution.
- the alkali metal hydroxide is, for example, sodium hydroxide or potassium hydroxide.
- a pH value in this specification is defined as a value measured when a temperature of a mixed solution is 40 °C.
- a pH of the mixed solution is measured when the temperature of the mixed solution sampled from a reaction tank reaches 40 °C. When the temperature of the sampled mixed solution is less than 40 °C, the mixed solution is heated to 40 °C and the pH of the mixed solution is measured. When the temperature of the sampled mixed solution exceeds 40 °C, the mixed solution is cooled to 40 °C and the pH of the mixed solution is measured.
- a complexing agent is continuously supplied to the reaction tank in addition to the nickel salt solution, the cobalt salt solution, and the manganese salt solution, nickel, cobalt, and manganese react to produce Ni a Co b Mn c (OH) 2 .
- a temperature of the reaction tank is controlled, for example, such that it is within the range of 20 °C or more and 80 °C or less, and preferably 30 °C or more and 70 °C or less.
- a pH value in the reaction tank is controlled, for example, such that it is within the range of pH 9 or more and pH 13 or less, and preferably pH 11 or more and pH 13 or less.
- reaction tank used in the continuous type co-precipitation method a reaction tank of a type in which the formed reaction precipitate overflows for separation can be used.
- various gases for example, inert gases such as nitrogen, argon, and carbon dioxide, oxidizing gases such as air and oxygen, or a mixed gas thereof may be supplied to the reaction tank and an oxidation state of the obtained reaction product may be controlled.
- inert gases such as nitrogen, argon, and carbon dioxide
- oxidizing gases such as air and oxygen, or a mixed gas thereof
- peroxides such as hydrogen peroxide, peroxide salts such as permanganates, perchlorates, hypochlorites, nitric acid, halogen, ozone, and the like can be used.
- organic acids such as oxalic acid and formic acid, sulfites, and hydrazine can be used.
- the inside of the reaction tank may be an inert atmosphere. If the inside of the reaction tank is an inert atmosphere, a metal which is more easily oxidized than nickel among metals contained in the mixed solution is prevented from agglomerating before nickel. For this reason, a uniform metal composite hydroxide is obtained.
- the inside of the reaction tank may be an appropriate oxidizing atmosphere.
- the oxidizing atmosphere may be an oxygen-containing atmosphere in which an oxidizing gas is mixed with an inert gas or an atmosphere in which an oxidizing agent is present in an inert gas atmosphere.
- an appropriate oxidizing atmosphere a transition metal contained in a mixed solution is oxidized and a form of a metal composite oxide is easily controlled.
- Oxygen and an oxidizing agent in an oxidizing atmosphere should have sufficient oxygen atoms to oxidize the transition metal.
- an atmosphere in the reaction tank can be controlled using a method such as passing an oxidizing gas through the inside of the reaction tank, bubbling an oxidizing gas in the mixed solution, or the like.
- a metal composite compound is obtained by washing the obtained reaction precipitate with water and then drying the reaction precipitate.
- a nickel-cobalt-manganese hydroxide is obtained as a metal composite compound.
- the reaction precipitate may be washed with a weak acid water or an alkaline solution.
- the alkaline solution include an aqueous solution containing sodium hydroxide and an aqueous solution containing potassium hydroxide.
- a pulverizing machine is preferably a grinding machine, and particularly preferably a stone mill type grinding machine.
- a stone mill type grinding machine it is desirable to adjust the clearance between an upper mill and a lower mill in accordance with an agglomerated state of a metal composite hydroxide.
- the clearance between the upper mill and the lower mill is preferably, for example, in the range of 10 ⁇ m or more and 200 ⁇ m or less.
- a nickel-cobalt-manganese composite hydroxide has been manufactured in the above example, a nickel-cobalt-manganese composite oxide may be prepared.
- a nickel-cobalt-manganese composite oxide by calciningcalcining a nickel-cobalt-manganese composite hydroxide.
- a calciningcalcining time it is desirable that the total time from the start of an increase in temperature to the completion of the temperature holding after reaching the temperature be one hour or more 30 hours or less.
- a rate of temperature increase in a heating process in which the temperature reaches a maximum holding temperature is preferably 180 °C/hour or more, more preferably 200 °C/hour or more, and particularly preferably 250 °C/hour or more.
- the maximum holding temperature in this specification is a maximum temperature of a holding temperature in an atmosphere in a calciningcalcining furnace in a calciningcalcining process and refers to a calciningcalcining temperature in the calciningcalcining process.
- the maximum holding temperature refers to a maximum temperature in the heating processes.
- the temperature increasing rate in this specification is calculated from a time from the start of increasing a temperature to reaching of a maximum holding temperature and a temperature difference between a temperature at the start of increase a temperature in the calciningcalcining furnace of a calciningcalcining device and a maximum holding temperature in the calciningcalcining device.
- a metal composite oxide or a metal composite hydroxide is mixed with a lithium salt. Furthermore, in this embodiment, it is desirable to mix in an inert fusing agent simultaneously with this mixing.
- a mixture containing a metal composite oxide, a lithium salt, and an inert fusing agent or a mixture containing a metal composite hydroxide, a lithium salt, and an inert fusing agent is calcined
- a mixture containing a metal composite compound and a lithium salt is calcined in the presence of the inert fusing agent. It is possible to prevent generation of secondary particles due to sintering of primary particles by calciningcalcining the mixture containing a metal composite compound and a lithium salt in the presence of an inert fusing agent. Furthermore, it is possible to promote growing of single particles.
- lithium salt any one of lithium carbonate, lithium nitrate, lithium acetate, lithium hydroxide, lithium hydroxide, lithium oxide, lithium chloride, and lithium fluoride or a combination of two or more of these can be used.
- lithium hydroxide and lithium carbonate are preferable.
- lithium hydroxide contains lithium carbonate as an impurity
- the content of lithium carbonate in the lithium hydroxide is preferably 5 mass% or less.
- drying conditions are not particularly limited.
- the drying conditions may be, for example, any of the following 1) to 3).
- an inert gas such as nitrogen, helium, or argon may be used in an atmosphere at the time of drying.
- oxygen or air may be used in an atmosphere at the time of drying.
- a reducing agent such as hydrazine and sodium sulfite may be used in an inert gas atmosphere at the time of drying.
- classification may be performed as appropriate.
- lithium contained in the lithium salt and a metal element contained in the metal composite compound are mixed at a ratio at which a molar ratio of lithium contained in the lithium salt and the metal element contained in the metal composite compound exceeds 1.
- a lithium-nickel-cobalt-manganese composite oxide is obtained by calcining the mixture of the nickel-cobalt-manganese composite compound and the lithium salt.
- dry air, an oxygen atmosphere, an inert atmosphere, or the like is used in accordance with a desired composition and a plurality of heating processes are performed if necessary.
- the mixture may be calcined in the presence of inert fusing agent. It is possible to promote reaction of the mixture by performing calcining in the presence of an inert fusing agent.
- the inert fusing agent may remain in the lithium metal composite oxide which has been subjected to calcining or may be removed by performing washing with water or alcohol after calcining.
- the calcined lithium metal composite oxide is preferably washed with water or alcohol.
- the holding temperature in the calcining may be adjusted in accordance with a type of transition metal element to be used, a precipitant, a type of inert fusing agent, and an amount.
- the holding temperature may be set in consideration of the melting point of an inert fusing agent to be described later and is preferably set in the range of the melting point of the inert fusing agent-200 °C or more and the melting point of the inert fusing agent+200 °C or less.
- the holding temperature include a range of 200 °C or more and 1150 °C or less, preferably a range of 300 °C or more and 1050 °C or less, or a range of 500 °C or more and 1000 °C or less.
- a holding time at the holding temperature is 0.1 hours or more and 20 hours or less, and preferably 0.5 hours or more and 10 hours or less.
- a temperature increasing rate to the holding temperature is generally 50 °C/hour or more and 400 °C/hour or less and a rate of temperature decrease from the holding temperature to room temperature is generally 10 °C/hour or more and 400 °C/hour or less.
- air, oxygen, nitrogen, argon, or a mixed gas thereof can be used as a calcining atmosphere.
- the lithium metal composite oxide obtained through calcining is classified after pulverization and a positive electrode active material capable of being applied to a lithium secondary battery is obtained.
- the "appropriate external force” refers to an external force which is sufficient to disperse agglomerations without damaging the crystallites of the lithium metal composite oxide.
- a grinding machine is preferably used, and particularly preferably a stone mill type grinding machine is used.
- a stone mill type grinding machine is used, it is desirable to adjust the clearance between an upper mill and a lower mill in accordance with an agglomerated state of the lithium metal composite oxide.
- the clearance between the upper mill and the lower mill is preferably, for example, in the range of 10 ⁇ m or more and 200 ⁇ m or less.
- the inert fusing agent which can be used in this embodiment is not particularly limited as long as it does not easily react with a mixture at the time of calcining.
- a salt of at least one element selected from the group consisting of Na, K, Rb, Cs, Ca, Mg, Sr, and Ba is used.
- one or more elements selected from the group consisting of Na, K, Rb, Cs, Ca, Mg, Sr, and Ba are referred to as "A.”
- the salt of A include one or more selected from the group consisting of fluorides, chlorides of A, carbonates of A, sulfates of A, nitrates of A, phosphates of A, hydroxides of A, molybdates of A, and tungstates of A.
- Examples of the fluorides of A include NaF (melting point: 993 °C), KF (melting point: 858 °C), RbF (melting point: 795 °C), CsF (melting point: 682 °C), CaF 2 (melting point: 1402 °C), MgF 2 (melting point: 1263 °C), SrF 2 (melting point: 1473 °C), and BaF 2 (melting point: 1355 °C).
- chlorides of A include NaCl (melting point: 801 °C), KC1 (melting point: 770 °C), RbCl (melting point: 718 °C), CsCl (melting point: 645 °C), CaCl 2 (melting point: 782 °C), MgCh (melting point: 714 °C), SrCl 2 (melting point: 857 °C), and BaCl 2 (melting point: 963 °C).
- Examples of the carbonates of A include Na 2 CO3 (melting point: 854 °C), K 2 CO 3 (melting point: 899 °C), Rb 2 CO 3 (melting point: 837 °C), Cs 2 CO 3 (melting point: 793 °C), CaCO 3 (melting point: 825 °C), MgCO 3 (melting point: 990 °C), SrCO 3 (melting point: 1497 °C), and BaCO3 (melting point: 1380 °C).
- Examples of the sulfates of A include Na 2 SO 4 (melting point: 884 °C), K 2 SO 4 (melting point: 1069 °C), Rb 2 SO 4 (melting point: 1066 °C), Cs 2 SO 4 (melting point: 1005 °C), CaSO 4 (melting point: 1460 °C), MgSO 4 (melting point: 1137 °C), SrSO 4 (melting point: 1605 °C), and BaSO 4 (melting point: 1580 °C).
- Examples of the nitrates of A include NaNO 3 (melting point: 310 °C), KNO 3 (melting point: 337 °C), RbNO 3 (melting point: 316 °C), CsNO 3 (melting point: 417 °C), Ca(NO 3 ) 2 (melting point: 561 °C), Mg(NO 3 ) 2 , Sr(NO 3 ) 2 (melting point: 645 °C), and Ba(NO 3 ) 2 (melting point: 596 °C).
- Examples of the phosphates of A include Na 3 PO 4 , K 3 PO 4 (melting point: 1340 °C), Rb 3 PO 4 , CS 3 PO 4 , Ca 3 (PO 4 ) 2 , Mg 3 (PO 4 ) 2 (melting point: 1184 °C), Sr 3 (PO 4 ) 2 (melting point: 1727 °C), and Ba 3 (PO 4 ) 2 (melting point: 1767 °C).
- hydroxides of A examples include NaOH (melting point: 318 °C), KOH (melting point: 360 °C), RbOH (melting point: 301 °C), CsOH (melting point: 272 °C), Ca(OH) 2 (melting point: 408 °C), Mg(OH) 2 (melting point: 350 °C), Sr(OH) 2 (melting point: 375 °C), and Ba(OH) 2 (melting point: 853 °C).
- Examples of the molybdates of A include Na 2 MoO 4 (melting point: 698 °C), K 2 MoO 4 (melting point: 919 °C), Rb 2 MoO 4 (melting point: 958 °C), Cs 2 MoO 4 (melting point: 956 °C), CaMoO 4 (melting point: 1520 °C), MgMoO 4 (melting point: 1060 °C), SrMoO 4 (melting point: 1040 °C), and BaMoO 4 (melting point: 1460 °C).
- Examples of the tungstates of A include Na 2 WO 4 (melting point: 687 °C), K 2 WO 4 , Rb 2 WO 4 , Cs 2 WO 4 , CaWO 4 , MgWO 4 , SrWO 4 , and BaWO 4 .
- two or more of these inert fusing agents can also be used.
- melting points of all of the inert fusing agents may be reduced in some cases.
- inert fusing agent configured to obtain a lithium metal composite oxide having higher crystallinity
- one or more salts selected from the group consisting of the carbonates of A, the sulfates of A, and the chlorides of A are preferable.
- A is preferably one or both of sodium (Na) and potassium (K).
- preferred inert fusing agents are one or more selected from the group consisting of NaCl, KCl, Na 2 CO 3 , K 2 CO 3 , Na 2 SO 4 , and K 2 SO 4 .
- an amount of inert fusing agents present at the time of calcining may be selected.
- the amount of inert fusing agents present at the time of calcining is preferably 0.1 parts by mass or more, and more preferably 1 part by mass or more with respect to 100 parts by mass of a lithium compound.
- an inert fusing agent other than the above-described inert fusing agents may be also be used. Examples of the inert fusing agent other than the above-described inert fusing agents include ammonium salts or the like such as NH 4 Cl and NH 4 F.
- a method for mixing a raw material for a coating material with the lithium metal composite oxide and causing the raw material for a coating material and the lithium metal composite oxide to react may be exemplified.
- a mixture of the raw material for a coating material and the lithium metal composite oxide may be subjected to a heating treatment.
- the lithium metal composite oxide constituting the particles of the lithium metal composite oxide and the lithium metal composite oxide constituting the coated layer are different oxides.
- the above-described lithium salts and oxides, hydroxides, carbonates, nitrates, sulfates, halides, oxalates, or alkoxides of at least one element selected from the group consisting of Nb, Ge, Si, P, Al, W, Ta, Ti, S, Zr, Zn, V, and B can be used.
- a compound containing at least one element selected from the group consisting of Nb, Ge, Si, P, Al, W, Ta, Ti, S, Zr, Zn, V, and B is preferably an oxide.
- Examples of the raw material for a coating material include aluminum oxide, aluminum hydroxide, aluminum sulfate, aluminum chloride, aluminum alkoxides, boron oxide, boric acid, and the like.
- aluminum oxide, aluminum hydroxide, boron oxide, boric acid, niobium oxide, lithium niobate, lithium borate, lithium phosphate, and lithium silicate are preferable.
- the raw material for a coating material preferably has particles finer than the secondary particles of the lithium metal composite oxide.
- an average secondary particle diameter of the raw material for a coating material is preferably 1 ⁇ m or less, and more preferably 0.1 ⁇ m or less.
- a lower limit of the average secondary particle diameter of the raw material for a coating material is preferably as small as possible.
- the lower limit of the average secondary particle diameter of the raw material for a coating material is, for example, 0.001 ⁇ m. It is possible to measure the average secondary particle diameter of the raw material for a coating material in the same manner as in the average secondary particle diameter of the lithium metal composite oxide.
- the raw material for a coating material and the lithium metal composite oxide are uniformly mixed until agglomerates of the raw material for a coating material and agglomerates of the lithium metal composite oxide disappear.
- a mixing device is not limited as long as it can uniformly mix the raw material for a coating material and the lithium metal composite oxide.
- a Loedige mixer is preferable.
- the coated layer it is possible to cause the coated layer to more firmly adhere to the surface of the lithium metal composite oxide by performing mixing in an atmosphere in which water or water and carbon dioxide gas are included.
- the coated layer After the mixing, it is possible to cause the coated layer to more firmly adhere to the surface of the lithium metal composite oxide also by holding the raw material for a coating material and the lithium metal composite oxide in an atmosphere in which water or water and carbon dioxide gas are included.
- the heat treatment conditions may be different in accordance with a type of raw material for a coating material in some cases.
- Examples of the heat treatment conditions include a heat treatment temperature and a heat treatment holding time.
- the raw material for a coating material when aluminum is used as the raw material for a coating material, it is desirable to perform calcining at a temperature in a range of 600 °C or more and 800 °C or less for four hours or more and 10 hours or less. It is possible to control a particle size in the range of Requirement 2 by performing calcining under the calcining conditions at a high temperature for a long time. If the calcining temperature is higher than 800 °C, the raw material for a coating material may form a solid solution with the lithium metal composite oxide and the coated layer may not be formed in some cases. If the calcining time is shorter than four hours, the raw material for a coating material may insufficiently diffuse and the coated layer may not be formed uniformly in some cases.
- the calcining temperature in this specification is a temperature that corresponds to a temperature in the atmosphere in the calcining furnace and is a maximum temperature at the holding temperature in this calcining process.
- the "maximum temperature at the holding temperature” may be referred to as a “maximum holding temperature.”
- a calcining temperature in each of the heating processes corresponds to a temperature at the time of performing heating at a maximum holding temperature.
- a technique for forming a coated layer it is possible to use a technique such as sputtering, chemical vapor deposition (CVD), vapor deposition, and spray coating. It is also possible to obtain a positive electrode active material for an all-solid-state lithium-ion battery by forming a coated layer on a surface of a lithium metal composite oxide through these techniques.
- CVD chemical vapor deposition
- spray coating it is also possible to obtain a positive electrode active material for an all-solid-state lithium-ion battery by forming a coated layer on a surface of a lithium metal composite oxide through these techniques.
- the positive electrode active material for an all-solid-state lithium-ion battery may be obtained by further adding a raw material for a coating material, mixing them together, and calcining them in some cases.
- the calcining temperature of the coated layer to be manufactured is lower than the calcining temperature of the lithium metal composite oxide to be manufactured, it is desirable to apply such a manufacturing method.
- a mixing process for mixing the metal composite compound and the lithium salt when the raw material for a coating material is further added, the raw material for a coating material, the metal composite compound, and the lithium salt are uniformly mixed until an agglomerate of the raw material for a coating material, an agglomerate of the metal composite compound, and an agglomerate of the lithium salt disappear.
- a mixing device is not limited as long as it can uniformly mix the raw material for a coating material, the metal composite compound, and the lithium salt.
- a Lodige mixer is preferable.
- the positive electrode active material for an all-solid-state lithium-ion battery is obtained by calcining the mixture of the raw material for a coating material, the metal composite compound, and the lithium salt under the calcining conditions of the coated layer described above and forming the coated layer on the surface of the lithium metal composite oxide.
- the positive electrode active material for an all-solid-state lithium-ion battery is obtained by crushing and classifying the particles of the coated layer formed on the surfaces of the primary particles or the secondary particles of the lithium metal composite oxide.
- a positive electrode active material in this embodiment includes single particles and secondary particles, it is possible to manufacture a positive electrode active material from the manufacturing method 1 for the positive electrode active material described above by performing the following changes.
- a metal composite compound forming the single particles finally and a metal composite compound forming the secondary particles finally are respectively manufactured.
- a metal composite compound which finally forms single particles may be referred to as a "single particle precursor” in some cases.
- a metal composite compound which finally forms secondary particles may be referred to as a "secondary particle precursor" in some cases.
- a first co-precipitation tank configured to manufacture a single particle precursor and a second co-precipitation tank configured to manufacture a secondary particle precursor are used.
- a temperature of the reaction tank is preferably 30 °C or more and 80 °C or less, more preferably controlled in the range of 40 °C or more and 70 °C or less, and further preferably in the range of ⁇ 20 °C with respect to that of a second reaction tank to be described later.
- a pH value in the reaction tank is preferably pH 10 or more and pH 13 or less, more preferably controlled in the range of pH 11 or more and pH 12.5 or less, further preferably within the range of ⁇ pH 2 with respect to that of a second reaction tank to be described later, and particularly preferably higher than a pH value of the second reaction tank.
- a second particle precursor by appropriately controlling a concentration of the metal salts supplied to the second co-precipitation tank, a stirring speed, a reaction temperature, a reaction pH, calcining conditions to be described later, and the like.
- a temperature of the reaction tank is preferably 20 °C or more and 80 °C or less, more preferably controlled in the range of 30 °C or more and 70 °C or less, and further preferably in the range of ⁇ 20 °C with respect to that of a second reaction tank to be described later.
- a pH value in the reaction tank is preferably pH 10 or more and pH 13 or less, more preferably controlled in the range of pH 11 or more and pH 12.5 or less, further preferably within the range of ⁇ pH 2 with respect to that of a second reaction tank to be described later, and particularly preferably higher than a pH value of the second reaction tank.
- a nickel-cobalt-manganese composite hydroxide is isolated by washing each of the reaction products obtained in this way with water and then drying it.
- the nickel-cobalt-manganese composite hydroxide to be isolated includes a single particle precursor and a secondary particle precursor.
- a nickel-cobalt-manganese composite oxide may be prepared.
- a nickel-cobalt-manganese composite oxide by calcining a nickel-cobalt-manganese composite hydroxide.
- the above-described conditions can be adopted as the calcining conditions of the nickel-cobalt-manganese composite hydroxide.
- the above-described metal composite oxide or metal composite hydroxide as the single particle precursor and the secondary particle precursor obtained in the above process is dried and then mixed with a lithium salt.
- the single particle precursor and the secondary particle precursor may be dried and then classified.
- the single particle precursor and the secondary particle precursor may be agglomerated or separated and secondary particles generated through agglomeration of the single particle precursor and single particles generated through separation of the secondary particle precursor may also be present. It is possible to control a presence ratio of the single particles and the secondary particles in the lithium metal composite oxide which is finally obtained by adjusting a mixing ratio of the single particle precursor and the secondary particle precursor and the process conditions of the processes subsequent to mixing.
- the positive electrode active material when a positive electrode active material in this embodiment includes single particles and secondary particles, the positive electrode active material can be manufactured by manufacturing respectively a first lithium metal composite oxide constituted of the single particles and a second lithium metal composite oxide constituted of the secondary particles through the manufacturing method 1 for the positive electrode active material described above and mixing the first lithium metal composite oxide and the second lithium metal composite oxide.
- the holding temperature at the time of calcining the first lithium metal composite oxide may be higher than the holding temperature at the time of calcining the second lithium metal composite oxide.
- the holding temperature of the first lithium metal composite oxide is higher than the holding temperature of the second lithium metal composite oxide by preferably 30 °C or higher, more preferably 50 °C or higher, and still more preferably 80 °C or higher.
- the lithium metal composite oxide containing the single particles and the secondary particles is obtained by mixing the first lithium metal composite oxide and the second lithium metal composite oxide which have been obtained at a predetermined ratio.
- a composition of the positive electrode active material in this embodiment can be confirmed by dissolving the particles of the positive electrode active material in hydrochloric acid and then performing composition analysis using an inductively coupled plasma emission spectrometer (for example, SPS3000 manufactured by SII Nano Technology Inc.).
- an inductively coupled plasma emission spectrometer for example, SPS3000 manufactured by SII Nano Technology Inc.
- the constitution of the all-solid-state lithium-ion battery will be described and the positive electrode using the positive electrode active material for an all-solid-state lithium-ion battery according to an aspect of the present invention as the positive electrode active material of the all-solid-state lithium-ion battery and the all-solid-state lithium-ion battery including the positive electrode will be described below.
- Figs. 2 and 3 are schematic diagrams illustrating an example of the all-solid-state lithium-ion battery in this embodiment.
- Fig. 2 is a schematic diagram illustrating a laminate included in the all-solid-state lithium-ion battery in this embodiment.
- Fig. 3 is a schematic diagram illustrating an overall constitution of the all-solid-state lithium-ion battery in this embodiment.
- the all-solid-state lithium-ion battery in this embodiment is a secondary battery.
- An all-solid-state lithium-ion battery 1000 includes a laminate 100 having a positive electrode 110, a negative electrode 120, and a solid electrolyte layer 130 and an exterior body 200 configured to accommodate the laminate 100.
- the laminate 100 may include an external terminal 113 connected to a positive electrode collector 112 and an external terminal 123 connected to a negative electrode collector 122.
- the solid electrolyte layer 130 is disposed between the positive electrode 110 and the negative electrode 120 so that the positive electrode 110 and the negative electrode 120 are not short-circuited each other.
- the all-solid-state lithium-ion battery 1000 may have a separator which is disposed between the positive electrode 110 and the negative electrode 120 and used in a conventional liquid-based lithium-ion secondary battery and prevent a short circuit between the positive electrode 110 and the negative electrode 120.
- the all-solid-state lithium-ion battery 1000 includes an insulator (not shown) configured to insulate between the laminate 100 and the exterior body 200 and a sealing body (not shown) configured to seal an opening portion 200a of the exterior body 200.
- a container formed of a highly corrosion-resistant metal material such as aluminum, stainless steel, and nickel-plated steel can be used as the exterior body 200. Furthermore, it is also possible to use a container obtained by processing a laminate film having at least one surface which has been subjected to a corrosion-resistant processing in a bag shape.
- Examples of a shape of the all-solid-state lithium-ion battery 1000 include shapes such as a coin shape, a button shape, a paper type (or a sheet type), a cylindrical shape, and an angular shape.
- the all-solid-state lithium-ion battery 1000 is illustrated as having one laminate 100, the present invention is not limited thereto.
- the all-solid-state lithium-ion battery 1000 may have a constitution in which a plurality of unit cells (the laminate 100) are sealed inside the exterior body 200 using the laminate 100 as a unit cell.
- the positive electrode 110 in this embodiment has a positive electrode active material layer 111 and the positive electrode collector 112.
- the positive electrode active material layer 111 includes the positive electrode active material which is the above aspect of the present invention. Furthermore, the positive electrode active material layer 111 may include a solid electrolyte (a second solid electrolyte), a conductive material, and a binder.
- the positive electrode active material included in the positive electrode active material layer 111 is in contact with the second solid electrolyte included in the positive electrode active material layer 111.
- the positive electrode active material layer 111 includes a plurality of particles (a positive electrode active material) including crystals of a lithium metal composite oxide and a solid electrolyte filling between a plurality of particles (a positive electrode active material) and in contact with the particles (a positive electrode active material).
- a solid electrolyte which may be included in the positive electrode active material layer 111 in this embodiment, a solid electrolyte having lithium ion conductivity and used for known all-solid-state batteries can be employed.
- a solid electrolyte include inorganic electrolytes and organic electrolytes.
- the inorganic electrolytes include oxide-based solid electrolytes, sulfide-based solid electrolytes, and hydride-based solid electrolytes.
- the organic electrolytes include polymer-based solid electrolytes.
- oxide-based solid electrolytes examples include perovskite type oxides, NASICON type oxides, LISICON type oxides, garnet type oxides, and the like.
- perovskite type oxides examples include Li-La-Ti-based oxides such as Li a La 1-a TiO 3 (0 ⁇ a ⁇ 1), Li-La-Ta-based oxides such as Li b La 1-b TaO 3 (0 ⁇ b ⁇ 1), Li-La-Nb-based oxides such as Li c La 1-c NbO 3 (0 ⁇ c ⁇ 1), and the like.
- Examples of the NASICON type oxides include Li 1+d Al d Ti 2-d (PO 4 ) 3 (0 ⁇ d ⁇ 1) and the like.
- the NASICON type oxides are oxides represented by Li m M 1 n M 2 o P p O q .
- M 1 indicates one or more elements selected from the group consisting of B, Al, Ga, In, C, Si, Ge, Sn, Sb, and Se.
- M 2 indicates one or more elements selected from the group consisting of Ti, Zr, Ge, In, Ga, Sn, and Al.
- m, n, o, p, and q are arbitrary integers.
- Examples of the LISICON type oxides include oxides and the like represented by Li 4 M 3 O 4 -Li 3 M 4 O 4 .
- M 3 indicates one or more elements selected from the group consisting of Si, Ge, and Ti.
- M 4 indicates one or more elements selected from the group consisting of P, As, and V.
- garnet type oxides examples include Li-La-Zr-based oxides and the like such as Li 7 La 3 Zr 2 O 12 (LLZ).
- the oxide-based solid electrolytes may be crystalline materials or non-crystalline (amorphous) materials.
- the non-crystalline (amorphous) solid electrolytes include Li-B-O compounds such as Li 3 BO 3 , Li 2 B 4 O 7 , and LiBO 2 . It is desirable that the oxide-based solid electrolytes contain a non-crystalline material.
- Examples of the sulfide-based solid electrolytes include Li 2 S-P 2 S 5 -based compounds, Li 2 S-SiS 2 -based compounds, Li 2 S-GeS 2 -based compounds, Li 2 S-B 2 S 3 -based compounds, Li 2 S-P 2 S 3 -based compounds, LiI-Si 2 S-P 2 S 5 , LiI-Li 2 S-P 2 O 5 , LiI-Li 3 PO 4 -P 2 S 5 , Li 10 GeP 2 S 12 , and the like.
- the expression "-based compounds” indicating sulfide-based solid electrolytes is used as a general expression for solid electrolytes mainly containing a raw material such as "Li 2 S” and "P 2 S 5 " described before "-based compounds.”
- Li 2 S-P 2 S 5 -basedcompounds include solid electrolytes containing Li 2 S and P 2 S 5 and further containing other raw materials.
- the Li 2 S-P 2 S 5 -based compounds also include solid electrolytes having different mixing ratio of Li 2 S and P 2 S 5 .
- Li 2 S-P 2 S 5 -basedcompounds examples include Li 2 S-P 2 S 5 , Li 2 S-P 2 S 5 -LiI, Li 2 S-P 2 S 5 -LiCl, Li 2 S-P 2 S 5 -LiBr, Li 2 S-P 2 S 5 -Li 2 O, Li 2 S-P 2 S 5 -Li 2 O-LiI, Li 2 S-P 2 S 5 -Z m S n (m and n are positive numbers: Z is Ge, Zn, or Ga), and the like.
- Li 2 S-SiS 2 -based compounds examples include Li 2 S-SiS 2 , Li 2 S-SiS 2 -LiI, Li 2 S-SiS 2 -LiBr, Li 2 S-SiS 2 -LiCl, Li 2 S-SiS 2 -B 2 S 3 -LiI, Li 2 S-SiS 2 -P 2 S 5 -LiI, Li 2 S-SiS 2 -Li 3 PO 4 , Li 2 S-SiS 2 -Li 2 SO 4 , Li 2 S-SiS 2 -Li x MO y (x and y are positive numbers: M is P, Si, Ge, B, Al, Ga, or In), and the like.
- Li 2 S-GeS 2 -based compounds examples include Li 2 S-GeS 2 , Li 2 S-GeS 2 -P 2 S 5 , and the like.
- the sulfide-based solid electrolyte may be a crystalline material or a non-crystalline (amorphous) material. It is desirable that the sulfide-based solid electrolytes include non-crystalline materials.
- Examples of materials for the hydride-based solid electrolytes include LiBH 4 , LiBH 4- 3KI, LiBH 4 -PI 2 , LiBH 4 -P 2 S 5 , LiBH 4 -LiNH 2 , 3LiBH 4 -LiI, LiNH 2 , Li 2 AlH 6 , Li(NH 2 ) 2 I, Li 2 NH, LiGd(BH 4 ) 3 Cl, Li 2 (BH 4 )(NH 2 ), Li 3 (NH 2 )I, Li 4 (BH 4 )(NH 2 ) 3 , and the like.
- polymer-based solid electrolytes examples include organic-based polymer electrolytes such as polyethylene-oxide-based polymer compounds and polymer compounds containing one or more selected from the group consisting of polyorganosiloxane chains and polyoxyalkylene chains.
- a so-called gel type polymer-based solid electrolyte in which a non-aqueous electrolytic solution is held in a polymer compound can also be used.
- the non-aqueous electrolytic solution included in the gel type polymer-based solid electrolyte loses fluidity and exhibits rigidity higher than that of the electrolytic solution.
- the rigidity of the electrolytic solution used for the liquid-based lithium-ion secondary battery is zero.
- the lithium-ion secondary battery using the gel type polymer-based solid electrolyte also corresponds to the all-solid-state lithium-ion battery of the present invention.
- the proportion of the polymer compounds contained in the solid electrolyte layer is preferably 1 mass% or more and 50 mass% or less.
- Two or more solid electrolytes can be used together as long as they do not impair the effects of the present invention.
- carbon materials or metal compounds can be used as a conductive material which may be included in the positive electrode active material layer 111 in this embodiment.
- the carbon materials include graphite powders, carbon blacks (for example, acetylene blacks), fibrous carbon materials, and the like. Since the carbon blacks are fine particles and have large surface areas, it is possible to increase the conductivity inside the positive electrode 110 and improve charge and discharge efficiency and output characteristics by adding an appropriate amount of carbon blacks to the positive electrode active material layer 111. On the other hand, if an amount of carbon blacks to be added is too large, both of the binding force between the positive electrode active material layer 111 and the positive electrode collector 112 and the binding force inside the positive electrode active material layer 111 decrease, which causes an increase in internal resistance.
- the metal compounds include metals, metal alloys, and metal oxides which have electrical conductivity.
- the ratio of the conductive materials in the positive electrode active material layer 111 is preferably 5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the positive electrode active material.
- fibrous carbon materials such as graphitized carbon fibers or carbon nanotubes are used as the conductive materials, the ratio thereof can be reduced.
- thermoplastic resins can be used as the binder.
- thermoplastic resins include polyimide resins, fluororesins such as polyvinylidene fluorides, polytetrafluoroethylenes, ethylene tetrafluoride/propylene hexafluoride/vinylidene fluoride-based copolymers, propylene hexafluoride/vinylidene fluoride-based copolymers, and ethylene tetrafluorides/perfluorovinyl ether-based copolymers; and polyolefin resins such as polyethylenes and polypropylenes.
- PVdF polyvinylidene fluorides
- PTFE polytetrafluoroethylene
- the positive electrode active material layer 111 have a high adhesive force between the positive electrode active material layer 111 and the positive electrode collector 112 and a high binding force inside the positive electrode active material layer 111 by making a ratio of fluororesins with respect to the entire positive electrode active material layer 111 have 1 mass% or more and 10 mass% or less, a ratio of polyolefin resins have 0.1 mass% or more and 2 mass% or less using the fluororesins and the polyolefin resins as a binder.
- the positive electrode active material layer 111 may be processed in advance as a sheet-like molded body containing a positive electrode active material and used as an "electrode" in the present invention. Furthermore, in the following description, such a sheet-like molded body may be referred to as a "positive electrode active material sheet" in some cases. A laminate obtained by laminating current collectors on a positive electrode active material sheet may be used as an electrode.
- the positive electrode active material sheet may include any one or more selected from the group consisting of the solid electrolyte, the conductive material, and the binder described above.
- the positive electrode active material sheet is obtained, for example, by mixing a positive electrode active material, a sintering auxiliary agent, the above-described conductive material, the above-described binder, a plasticizer, and a solvent, preparing a slurry thereof, applying the obtained slurry above a carrier film, and drying the slurry.
- Examples of the sintering auxiliary agent include Li 3 BO 3 or Al 2 O 3 .
- plasticizer examples include dioctyl phthalate.
- solvent examples include acetone, ethanol, and N-methyl-2-pyrrolidone.
- the slurry When the slurry is prepared, a ball mill can be used for mixing. Since the obtained mixture contains air bubbles mixed at the time of mixing in many cases, air bubbles may be removed under reduced pressure. If air bubble removal is performed, a part of the solvent volatilizes and the slurry is concentrated. Thus, the slurry has a high viscosity.
- the slurry can be applied using a known doctor blade.
- a PET film can be used as the carrier film.
- the positive electrode active material sheet obtained after drying is detached from the carrier film, processed into a required shape through punching, and used. Furthermore, the positive electrode active material sheet may be uniaxially pressed in a thickness direction.
- a sheet-like member having a metal material such as Al, Ni, stainless steel, and Au as a forming material can be used. It is desirable though to use Al as a material to form a thin film shape in that it is easy to process and inexpensive.
- a method for forming the positive electrode active material layer 111 above the positive electrode collector 112 under pressure can be used.
- a cold press or a hot press can be used for the forming under pressure.
- the positive electrode active material layer 111 may also be supported on the positive electrode collector 112 by pasting a mixture of a positive electrode active material, a solid electrolyte, a conductive material, and a binder into a positive electrode mixture using an organic solvent, applying the obtained positive electrode mixture on at least one surface side of the positive electrode collector 112 into a positive electrode mixture, drying it, pressing it, and fixing it.
- the positive electrode active material layer 111 may be supported on the positive electrode collector 112 by pasting a mixture of a positive electrode active material, a solid electrolyte, and a conductive material using an organic solvent, applying the obtained positive electrode mixture on at least one surface side of the positive electrode collector 112 using it as a positive electrode mixture, drying it, and sintering it.
- organic solvent which can be used for the positive electrode mixture examples include amine-based solvents such as N, N-dimethylaminopropylamine and diethylenetriamine; ether-based solvents such as tetrahydrofuran; ketone-based solvents such as methyl ethyl ketone; ester-based solvents such as methyl acetate; and amide-based solvents such as dimethylacetamide and N-methyl-2-pyrrolidone.
- NMP N-methyl-2-pyrrolidone may be referred to as "NMP" in some cases.
- Examples of a method for applying a positive electrode mixture on the positive electrode collector 112 include a slit die coating method, a screen coating method, a curtain coating method, a knife coating method, a gravure coating method, and an electrostatic spray method.
- the negative electrode 120 includes a negative electrode active material layer 121 and the negative electrode collector 122.
- the negative electrode active material layer 121 contains a negative electrode active material.
- the negative electrode active material layer 121 may contain a solid electrolyte and a conductive material. As the solid electrolyte, the conductive material, and the binder, those described above can be used.
- Examples of the negative electrode active material included in the negative electrode active material layer 121 include materials which are carbon materials, chalcogen compounds (oxides, sulfides, and the like), nitrides, metals, or alloys and to/from which lithium ions can be doped and undoped at a potential lower than that of the positive electrode 110.
- Examples of the carbon materials which can be used as the negative electrode active material include graphite such as natural graphite and artificial graphite, cokes, carbon blacks, pyrolytic carbons, carbon fibers, and organic polymer compound calcined bodies.
- oxides which can be used as the negative electrode active material include silicon oxides represented by the formula SiO x (where x is a positive real number) such as SiO 2 and SiO; titanium oxides represented by the formula TiO x (where x is a positive real number) such as TiO 2 and TiO; vanadium oxides represented by the formula VO x (where x is a positive real number) such as V 2 O 5 and VO 2 ; iron oxides represented by the formula FeO x (where x is a positive real number) such as Fe 3 O 4 , Fe 2 O3, and FeO; tin oxides represented by the formula SnO x (where x is a positive real number) such as SnO 2 and SnO; tungsten oxide represented by the general formula WO x (where x is a positive real number) such as WO 3 and WO 2 ; and metal composite oxides containing lithium and titanium or vanadium such as Li 4 Ti 5 O 12 and LiVO 2 .
- SiO x
- Examples of the sulfide which can be used as the negative electrode active material include titanium sulfides represented by the formula TiS x (where x is a positive real number) such as Ti 2 S 3 , TiS 2 , and TiS; vanadium sulfides represented by the formula VS x (where x is a positive real number) such as V 3 S 4 , VS 2 , and VS; iron sulfides represented by the formula FeS x (where x is a positive real number) such as Fe 3 S 4 , FeS 2 , and FeS; molybdenum sulfides represented by the formula MoS x (where x is a positive real number) such as Mo 2 S 3 and MoS 2 ; tin sulfides represented by the formula SnS x (where x is a positive real number) such as SnS 2 and SnS; tungsten sulfides represented by the formula WS x (where x is a positive real number)
- These carbon materials, oxides, sulfides, and nitrides may be used independently or a combination of two or more thereof may be used. Furthermore, these carbon materials, oxides, sulfides, and nitrides may be either crystalline or non-crystalline.
- examples of the metals which can be used as the negative electrode active material include lithium metals, silicon metals, tin metals, and the like.
- alloys which can be used as the negative electrode active material include lithium alloys such as Li-Al, Li-Ni, Li-Si, Li-Sn, and Li-Sn-Ni; silicon alloys such as Si-Zn; tin alloys such as Sn-Mn, Sn-Co, Sn-Ni, Sn-Cu, and Sn-La; and alloys such as Cu 2 Sb and La 3 Ni 2 Sn 7 .
- These metals and alloys are mainly used independently as electrodes, for example, after being processed into a foil shape.
- carbon materials having graphite such as natural graphite and artificial graphite as main components be used.
- a shape of the carbon materials may be any of, for example, a flake shape such as natural graphite, a spherical shape such as mesocarbon microbeads, a fibrous shape such as graphitized carbon fibers or an agglomerate of fine powders.
- oxides be used.
- a fibrous form or an agglomerate of fine powders be used.
- Examples of the negative electrode collector 122 included in the negative electrode 120 include a band-shaped member formed of a metal material such as Cu, Ni, and stainless steel. It is desirable though to use Cu as a forming material and process it into a thin film shape in that it is difficult to form an alloy with lithium and is easy to process.
- Examples of the method for supporting the negative electrode active material layer 121 on the negative electrode collector 122 include a method for performing forming under pressure, a method for applying a paste-like negative electrode mixture including a negative electrode active material above the negative electrode collector 122, drying them, and pressing them, and a method for applying a paste-like negative electrode mixture including a negative electrode active material above the negative electrode collector 122, drying them, and sintering them, as in the case of the positive electrode 110.
- the solid electrolyte layer 130 includes the above-described solid electrolyte (the first solid electrolyte).
- the solid electrolyte (the first solid electrolyte) constituting the solid electrolyte layer 130 and the solid electrolyte (the second solid electrolyte) included in the positive electrode active material layer 111 may be made of the same material.
- the solid electrolyte layer 130 functions as a medium for transmitting lithium ions and also functions as a separator configured to divide between the positive electrode 110 and the negative electrode 120 and prevent a short circuit.
- the solid electrolyte layer 130 can be formed by depositing an inorganic solid electrolyte on a surface of the positive electrode active material layer 111 included in the positive electrode 110 described above through a sputtering method.
- the solid electrolyte layer 130 can also be formed by applying a paste-like mixture including a solid electrolyte on a surface of the positive electrode active material layer 111 included in the positive electrode 110 described above and drying them.
- the solid electrolyte layer 130 may also be formed by performing drying, performing forming under pressure, and performing pressing through cold isostatic pressing (CIP).
- the solid electrolyte layer 130 can be formed by forming a solid electrolyte to have a pellet shape in advance, causing the pellet of the solid electrolyte and the above-described positive electrode active material sheet to overlap, and pressing them uniaxially in a lamination direction.
- the positive electrode active material sheet serves as the positive electrode active material layer 111.
- the positive electrode collector 112 is further disposed to the positive electrode active material layer 111 with respect to the obtained laminate of the positive electrode active material layer 111 and the solid electrolyte layer 130.
- the solid electrolyte layer 130 and the positive electrode 110 can be formed through uniaxial pressing in the lamination direction and further sintering.
- the positive electrode 110 in this way is in contact with the solid electrolyte layer 130.
- the solid electrolyte layer 130 has a first solid electrolyte.
- the positive electrode 110 has the positive electrode active material layer 111 in contact with the solid electrolyte layer 130 and the positive electrode collector 112 on which the positive electrode active material layer 111 is laminated.
- the positive electrode active material layer 111 includes a plurality of particles including crystals of a lithium metal composite oxide (that is, a positive electrode active material which is an aspect of the present invention) and a solid electrolyte (a second solid electrolyte) filling between the plurality of particles and in contact with the particles.
- the solid electrolyte and the particles included in the positive electrode active material layer 111 are in contact with the solid electrolyte layer 130. That is to say, the particles included in the positive electrode active material layer 111 are in contact with the solid electrolyte and the solid electrolyte layer 130 included in the positive electrode active material layer 111.
- the particles (the positive electrode active material) included in the positive electrode active material layer 111 be in contact with the solid electrolyte and the solid electrolyte layer 130 included in the positive electrode active material layer 111.
- the positive electrode active material included in the positive electrode active material layer 111 is in contact with the solid electrolyte included in the positive electrode active material layer 111.
- the positive electrode active material included in the positive electrode active material layer 111 is brought into conduction with the solid electrolyte included in the positive electrode active material layer 111.
- the positive electrode active material included in the positive electrode active material layer 111 is in contact with the solid electrolyte layer 130.
- the positive electrode active material included in the positive electrode active material layer 111 is brought into conduction with the solid electrolyte layer 130.
- the solid electrolyte included in the positive electrode active material layer 111 is in contact with the solid electrolyte layer 130.
- the solid electrolyte included in the positive electrode active material layer 111 is brought into conduction with the solid electrolyte layer 130.
- the positive electrode active material included in the positive electrode active material layer 111 is directly or indirectly brought into conduction with the solid electrolyte layer 130.
- the laminate 100 can be manufactured by laminating the negative electrode 120 on the solid electrolyte layer 130 provided above the positive electrode 110 as described above in a posture in which the negative electrode electrolyte layer121 is in contact with a surface of the solid electrolyte layer 130 using a known method.
- the solid electrolyte layer 130 is in contact with and brought in conduction with the negative electrode active material layer 121.
- the obtained all-solid-state lithium-ion battery 100 is provided by bringing the solid electrolyte layer 130 into contact with the positive electrode 110 and the negative electrode 120 so that the positive electrode 110 and the negative electrode 120 are not short-circuited.
- the provided all-solid-state lithium-ion battery 100 is charged by being connected to an external power supply and applying a negative potential to the positive electrode 110 and a positive potential to the negative electrode 120.
- the charged all-solid-state lithium-ion battery 100 is discharged by connecting a discharge circuit to the positive electrode 110 and the negative electrode 120 and supplying electricity to the discharge circuit.
- the electrode constituted as described above since the above-described positive electrode active material for an all-solid-state lithium-ion battery is provided, it is possible to improve the battery performance of the all-solid-state lithium-ion battery.
- the present invention also includes the following aspects.
- (3-3-4) The positive electrode according to any one of (3-3), (3-3-1), and (3-3-2), wherein a relational expression 0.91 ⁇ (D90-D10)/D50 ⁇ 10.0 holds.
- a positive electrode in contact with a solid electrolyte layer wherein the positive electrode includes a positive electrode active material layer in contact with the solid electrolyte layer and a current collector on which the positive electrode active material layer is laminated, the positive electrode active material layer includes a plurality of particles including crystals of a lithium metal composite oxide and a solid electrolyte filling between the plurality of particles and in contact with the particles, the solid electrolyte and the particles included in the positive electrode active material layer are in contact with the solid electrolyte layer, the lithium metal composite oxide has a layered structure and includes at least Li and a transition metal, when particle diameters in which a cumulative proportion from a small particle side are 10%, 50%, and 90% with respect to a cumulative particle size distribution based on a volume measured through a laser diffraction type particle size distribution measurement are assumed to be D10, D50, and D90, the particles are formed so that a relational expression (D90-D10)/D50 ⁇ 0.90 holds, and the crystals are formed so that
- An all-solid-state lithium-ion battery including the positive electrode active material according to any one of (3-1), (3-1-1), (3-1-2), and (3-2-3) or the positive electrode according to any one of (3-2), (3-2-1), (3-2-2), (3-2-3), (3-3-1), (3-3-2), (3-3-3), (3-3-4), (3-4-1), (3-4-2), (3-4-3), and (3-4-4).
- a method for charging an all-solid-state lithium-ion battery which includes providing a solid electrolyte layer such that the solid electrolyte layer is in contact with a positive electrode and a negative electrode so that a positive electrode and a negative electrode are not short-circuited and applying a negative potential to the positive electrode and a positive potential to the negative electrode using an external power supply, wherein the positive electrode includes particles including crystals of a lithium metal composite oxide, the lithium metal composite oxide has a layered structure and includes at least Li and a transition metal, when particle diameters in which a cumulative proportion from a small particle side are 10%, 50%, and 90% with respect to a cumulative particle size distribution based on a volume measured through a laser diffraction type particle size distribution measurement are assumed to be D10, D50, and D90, the particles are formed so that a relational expression (D90-D10)/D50 ⁇ 0.90 holds, and the crystals are formed so that a ratio ⁇ / ⁇ between a crystallite size ⁇ at a peak in the range
- (4-1-1) The method for charging an all-solid-state lithium-ion battery according to (4-1), wherein the solid electrolyte layer includes an oxide solid electrolyte.
- (4-1-2) The method for charging an all-solid-state lithium-ion battery according to (4-1) or (4-1-1), wherein a relational expression 0.91 ⁇ (D90-D10)/D50 ⁇ 11.0 holds.
- a method for discharing an all-solid-state lithium-ion battery including providing a solid electrolyte layer such that the solid electrolyte layer is in contact with a positive electrode and a negative electrode so that a positive electrode and a negative electrode are not short-circuited, charging the all-solid-state lithium-ion battery by applying a negative potential to the positive electrode and a positive potential to the negative electrode using an external power supply, and connecting a discharge circuit to the positive electrode and the negative electrode of the charged all-solid-state lithium-ion battery, wherein the positive electrode includes particles including crystals of a lithium metal composite oxide, the lithium metal composite oxide has a layered structure and includes at least Li and a transition metal, when particle diameters in which a cumulative proportion from a small particle side are 10%, 50%, and 90% with respect to a cumulative particle size distribution based on a volume measured through a laser diffraction type particle size distribution measurement are assumed to be D10, D50, and D90, the particles are formed so that a relational expression (D
- a ratio (D 90 /D 10 ) between a 90% cumulative volume particle size D 90 and a 10% cumulative volume particle size D 10 of a positive electrode active material was calculated through the following method.
- a dispersion solution was obtained by adding 0.1 g of a positive electrode active material to 50 ml of a 0.2 mass% aqueous sodium hexametaphosphate solution and dispersing powders of the positive electrode active material.
- a cumulative particle size distribution curve based on a volume was obtained by measuring a particle size distribution of the obtained dispersion solution using a laser diffraction scattering particle size distribution measurement device (Micro Truck MT3300EXII manufactured by MicrotracBEL Corp.).
- a value of a particle diameter when viewed a fine particle side at the time of 10% accumulation was assumed to be a 10% cumulative volume particle size D 10 (unit: ⁇ m)
- a value of a particle diameter when viewed from a fine particle side at the time of 50% accumulation was assumed to be a 50% cumulative volume particle size D 50 (unit: ⁇ m)
- a value of a particle diameter when viewed from a fine particle side at the time of 90% accumulation was assumed to be a 90% cumulative volume particle size D 90 (unit: ⁇ m)
- a ratio (D 90 -D 10 )/D 50 was calculated.
- a powder X-ray diffraction measurement of a positive electrode active material was performed using an X-ray diffraction measurement device (X'Pert PRO manufactured by PANalytical).
- a crystallite size ⁇ and a crystallite size ⁇ were calculated through the Scherrer equation using the obtained half-widths.
- a crystallite size ratio ⁇ / ⁇ was obtained from the obtained crystallite sizes ⁇ and ⁇ .
- a mixed raw material solution was prepared by mixing an aqueous nickel sulfate solution, an aqueous cobalt sulfate solution, and an aqueous manganese sulfate solution at a ratio of an atomic ratio of nickel atoms, cobalt atoms, and manganese atoms of 0.50:0.20:0.30.
- Nickel-cobalt-manganese composite hydroxide particles were obtained by adding an aqueous sodium hydroxide solution dropwise at appropriate times so that a pH of the solution in the reaction tank was 11.1.
- Nickel-cobalt-manganese composite hydroxide 1 was obtained by washing the nickel-cobalt-manganese composite hydroxide particles, removing water from the nickel-cobalt-manganese composite hydroxide particles using a centrifuge, washing the obtained solid, removing water from the obtained solid, and drying the obtained solid at 120 °C.
- a mixed raw material solution 2 was prepared by mixing an aqueous nickel sulfate solution, an aqueous cobalt sulfate solution, and an aqueous manganese sulfate solution at a ratio of an atomic ratio of nickel atoms, cobalt atoms, and manganese atoms of 0.55:0.20:0.25.
- Nickel-cobalt-manganese composite hydroxide particles were obtained by adding an aqueous sodium hydroxide solution dropwise at appropriate times so that a pH of the solution in the reaction tank was 12.0.
- Nickel-cobalt-manganese composite hydroxide 2 was obtained by washing the obtained nickel-cobalt-manganese composite hydroxide particles, removing water from the obtained nickel-cobalt-manganese composite hydroxide particles using a centrifuge, washing the obtained solid, removing water from the obtained solid, and drying the obtained solid at 120 °C.
- a lithium metal composite oxide was obtained by calcining the obtained mixture at 650 °C for five hours in an oxygen atmosphere, calcining the obtained mixture at 960 °C for five hours in an oxygen atmosphere, and calcining the obtained mixture at 400 °C for five hours in an air atmosphere.
- the obtained lithium metal composite oxide was used as a positive electrode active material 2.
- a lithium metal composite oxide was obtained by calcining the obtained mixture at 650 °C for five hours in an oxygen atmosphere, calcining the obtained mixture at 1015 °C for five hours in an air atmosphere, and calcining the obtained mixture at 400 °C for five hours in an oxygen atmosphere.
- the obtained lithium metal composite oxide was pulverized using a pin mill type pulverizing machine (Impact Mill AVIS 100 manufactured by Mill System Co., Ltd.) and then sieved using a turbo screener (TS 125 ⁇ 200 type manufactured by Freund Turbo Co., Ltd.). Operation conditions of the pin mill type pulverizing machine and the turbo screener were as follows.
- a positive electrode active material 3 was obtained by collecting powders passing through a screen in the turbo screener.
- D 50 was 5.41 and (D 90 -D 10 )/D 50 was 0.90.
- Nickel-cobalt-manganese composite hydroxide 4 was obtained as in Example 1 except that a mixed raw material solution was obtained by mixing an aqueous nickel sulfate solution, an aqueous cobalt sulfate solution, and an aqueous manganese sulfate solution at a ratio of an atomic ratio of nickel atoms, cobalt atoms, and manganese atoms of 0.88:0.08:0.04 and an aqueous sodium hydroxide solution was added dropwise at appropriate times so that a pH of the solution in a reaction tank was 12.4.
- a mixture 4 including a lithium metal composite oxide was obtained by calcining the obtained mixture at 800 °C for ten hours in an oxygen atmosphere.
- the mixture 4 and pure water at 5 °C were mixed at a ratio at which a ratio of the mixture 4 to a total amount of the mixture 4 and the pure water was 30 mass% and the obtained slurry was stirred for ten minutes.
- a positive electrode active material 4 was obtained by removing water from the solid substance again, vacuum-drying the solid substance at 80 °C for 15 hours, and vacuum-drying the solid substance at 150 °C for eight hours.
- a precipitate including nickel-cobalt-manganese composite hydroxide was obtained as in Example 4 except that an aqueous sodium hydroxide solution was added dropwise at appropriate times so that a ph of the solution in a reaction tank is 11.2 and a liquid temperature was maintained at 70 °C.
- Nickel-cobalt-manganese composite hydroxide 5 was obtained by pulverizing the obtained precipitate using a counter jet mill (100AFG type manufactured by Hosokawa Micron Corporation). Operation conditions of the counter jet mill were as follows.
- Nickel-cobalt-manganese composite hydroxide 6 was obtained as in Example 4 except that a mixed raw material solution was obtained by mixing an aqueous nickel sulfate solution, an aqueous cobalt sulfate solution, and an aqueous manganese sulfate solution at a ratio of an atomic ratio of nickel atoms, cobalt atoms, and manganese atoms of 0.91:0.07:0.02 and an aqueous sodium hydroxide solution was added dropwise at appropriate times so that a pH of the solution in a reaction tank was 12.3.
- a mixture 6 including a lithium metal composite oxide was obtained by calcining the obtained mixture at 790 °C for ten hours in an oxygen atmosphere.
- the mixture 6 and pure water at 5 °C were mixed at a ratio at which a ratio of the mixture 6 to a total amount of the mixture 6 and the pure water was 30 mass% and the obtained slurry was stirred for ten minutes.
- a positive electrode active material 6 was obtained by sieving the obtained powders using a turbo screener (manufactured by Freund Turbo Co., Ltd.). Operation conditions and sieving conditions of the turbo screener were the same as in Example 3.
- a commercially available LiCoO 2 was evaluated as a positive electrode active material E1.
- a commercially available LiNi 0.33 Co 0.33 Mn 0.33 O 2 was evaluated as a positive electrode active material E2.
- D 50 was 4.79 and (D 90 ⁇ D 10 )/D 50 was 0.89.
- a resin binder ethyl celulose
- a plasticizer dioctyl phthalate
- a solvent acetone
- a positive electrode mixture slurry was obtained by removing water from the obtained slurry using a planetary stirring and air bubble removal device.
- a positive electrode film with a thickness of 50 ⁇ m was formed by applying the obtained positive electrode mixture slurry above a PET film using a doctor blade and drying the coated film.
- a positive electrode active material sheet with a thickness of 40 ⁇ m was obtained by detaching the positive electrode film from the PET film, punching the positive electrode film to have a circle with a diameter of 14.5 mm, and uniaxially pressing the positive electrode film in a thickness direction thereof at 20MPa for one minute.
- Li 3 BO 3 included in the positive electrode active material sheet functions as a solid electrolyte in contact with the positive electrode active material in the positive electrode active material sheet. Furthermore, Li 3 BO 3 functions as a binder configured to hold the positive electrode active material in the positive electrode active material sheet.
- a laminate was obtained by laminating the positive electrode active material sheet and a solid electrolyte pellet made of Li 6.75 L a3 Zr 1.75 Nb 0.25 O 12 (manufactured by Toshima Seisakusho Co., Ltd.) and uniaxially pressing the laminate parallel to the lamination direction.
- the used solid electrolyte pellet had a diameter of 14.5 mm and a thickness of 0.5 mm.
- Organic components were burned off by causing the positive electrode active material sheet of the obtained laminate and a positive electrode collector (a gold foil; a thickness of 500 ⁇ m) to overlap and heating the laminate of the solid electrolyte, the positive electrode active material sheet, and the positive electrode collector at 300 °C for one hour in a state in which the laminate was pressed at 100 gf. Furthermore, a laminate of the solid electrolyte layer and the positive electrode was obtained by heating the laminate of the solid electrolyte, the positive electrode active material sheet, and the positive electrode collector to 800 °C at 5 °C/min and sintering the laminate of the solid electrolyte, the positive electrode active material sheet, and the positive electrode collector at 800 °C for one hour.
- the positive electrode active material sheet and the positive electrode collector constitute a positive electrode.
- An all-solid-state lithium-ion battery was prepared by placing the positive electrode on a lower lid of coin-type battery R2032 parts (manufactured by Hosen Co., Ltd.), causing it and the wave washer to overlap, using it as an upper lid, and performing caulking using a caulking machine for the laminate obtained by causing the positive electrode, the negative electrode, the negative electrode collector, and the wave washer to overlap.
- a charge and discharge test was performed under the following conditions using half cells prepared through the above-described method and initial charge and discharge efficiency was calculated.
- a conductive material an acetylene black
- PVdF binder
- a positive electrode for a lithium secondary battery was obtained by applying the obtained positive electrode mixture on an Al foil with a thickness of 40 ⁇ m serving as a current collector and vacuum-drying it at 150 °C for eight hours.
- An electrode area of the positive electrode for a lithium secondary battery was 1.65 cm 2 .
- the positive electrode for a lithium secondary battery prepared in "Preparation of the positive electrode for a lithium secondary battery” was placed on a lower lid of coin-type battery R2032 parts (manufactured by Hosen Co., Ltd.) so that a surface of an aluminum foil faces downward and a separator was placed thereabove.
- the separator was a porous film made of polyethylene.
- a lithium secondary battery was prepared by using a metal lithium as a negative electrode, placing the negative electrode on an upper side of a laminated film separator, using it as an upper lid via a gasket, and performing caulking using a caulking machine.
- the obtained lithium secondary battery was an R2032 coin type half cell.
- Tables 1 to 4 show measurement values of positive electrode active materials and Table 3 shows results of the evaluation of the physical properties of an all-solid-state lithium-ion battery using each positive electrode active material.
- “Me” in “Li/Me” mentioned in Table 1 indicates an amount of remaining metals excluding Li among metals included in a lithium metal composite oxide constituting a positive electrode active material. “Me” specifically indicates a total amount of Ni, Co, Mn, and M. Furthermore, “ND” in Table 1 indicates “no data.”
- Table 4 shows the results of evaluating the physical properties of a liquid-based lithium-ion secondary battery using each positive electrode active material. The results shown in Table 4 are reference examples.
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JP6726102B2 (ja) * | 2014-10-15 | 2020-07-22 | 住友化学株式会社 | リチウム二次電池用正極活物質、リチウム二次電池用正極及びリチウム二次電池 |
JP6621443B2 (ja) | 2016-07-06 | 2019-12-18 | 富士フイルム株式会社 | 固体電解質組成物、固体電解質含有シートおよび全固体二次電池ならびに固体電解質含有シートおよび全固体二次電池の製造方法 |
EP3509139A4 (fr) * | 2016-08-30 | 2019-08-28 | FUJIFILM Corporation | Composition d'électrolyte solide, feuille contenant un électrolyte solide, batterie secondaire entièrement solide, procédé de production d'une feuille contenant un électrolyte solide, et procédé de production d'une batterie secondaire entièrement solide |
JP2019066770A (ja) | 2017-10-04 | 2019-04-25 | シャープ株式会社 | 表示駆動装置および表示装置 |
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2019
- 2019-03-29 JP JP2019066770A patent/JP6650064B1/ja active Active
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2020
- 2020-01-17 WO PCT/JP2020/001480 patent/WO2020202708A1/fr unknown
- 2020-01-17 KR KR1020207015125A patent/KR102247128B1/ko active IP Right Grant
- 2020-01-17 EP EP20727134.7A patent/EP3920275A4/fr active Pending
- 2020-01-17 CN CN202080000842.0A patent/CN111971821A/zh active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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EP4382489A1 (fr) * | 2022-12-07 | 2024-06-12 | Samsung SDI Co., Ltd. | Matériau actif positif pour batteries au lithium rechargeables, son procédé de préparation et batteries au lithium rechargeables le comprenant |
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JP6650064B1 (ja) | 2020-02-19 |
KR20200117977A (ko) | 2020-10-14 |
JP2020167042A (ja) | 2020-10-08 |
CN111971821A (zh) | 2020-11-20 |
EP3920275A4 (fr) | 2022-06-01 |
WO2020202708A1 (fr) | 2020-10-08 |
KR102247128B1 (ko) | 2021-04-30 |
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